CN107020075A - Carbon dioxide electrochemical reduction simple substance bismuth catalyst and its preparation and application - Google Patents
Carbon dioxide electrochemical reduction simple substance bismuth catalyst and its preparation and application Download PDFInfo
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- CN107020075A CN107020075A CN201710204688.9A CN201710204688A CN107020075A CN 107020075 A CN107020075 A CN 107020075A CN 201710204688 A CN201710204688 A CN 201710204688A CN 107020075 A CN107020075 A CN 107020075A
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- carbon dioxide
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- electrochemical reduction
- dioxide electrochemical
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 75
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 60
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 23
- 239000000126 substance Substances 0.000 title abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 150000002739 metals Chemical class 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 7
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000009792 diffusion process Methods 0.000 claims description 21
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 17
- 238000001291 vacuum drying Methods 0.000 claims description 15
- 239000012018 catalyst precursor Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- 229910001868 water Inorganic materials 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229920000557 Nafion® Polymers 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 1
- 239000002243 precursor Substances 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 238000006722 reduction reaction Methods 0.000 abstract description 55
- 238000005406 washing Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 239000013078 crystal Substances 0.000 abstract 1
- 239000012265 solid product Substances 0.000 abstract 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 12
- XWNOTOKFKBDMAP-UHFFFAOYSA-N [Bi].[N+](=O)(O)[O-] Chemical compound [Bi].[N+](=O)(O)[O-] XWNOTOKFKBDMAP-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 235000019253 formic acid Nutrition 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 241000790917 Dioxys <bee> Species 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- -1 CO and methane Chemical class 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Catalysts (AREA)
Abstract
The invention provides the preparation of carbon dioxide electrochemical reduction catalyst and application, described carbon dioxide electrochemical reduction catalyst is characterized in that, including micro-nano simple substance bismuth catalyst, described micro-nano simple substance bismuth catalyst is synthesized by chemistry of aqueous solution restoring method, and preparation method includes：Bismuth nitrate and hydrazine hydrate mixed solution are heated and refluxed for, chemical reduction reaction is carried out, after solid product washing is centrifuged, micro-nano elemental metals bismuth is dried in vacuo to obtain, with distinct (012) crystal face.The micro-nano elemental metals bismuth catalyst of the present invention has high catalytic activity and selectivity to carbon dioxide reduction, and required overpotential is low, improves energy efficiency.In addition, the method for preparing catalyst of the present invention is simple to operate, mild condition, yield are high, it is easy to industrialized production.
Description
Technical field
Prepared the invention belongs to carbon dioxide electrochemical reduction catalyst and application field, it is more particularly to a kind of efficient micro-
Receive grade simple substance bismuth catalyst preparation and its application in Carbon dioxide electrochemical reduction.
Background technology
With developing rapidly for industry, on the one hand a large amount of primary energy such as fuel consumption such as coal, oil, natural gas produces
Worldwide shortage of resources, the opposing party CO are given birth to2The excessive emissions of isothermal chamber gas cause nature is flat to be difficult to bear very much
Environmental pollution.Carbon emission is reduced, the new energy of substitute fossil fuels is found, it has also become the focus of current global concern.CO2Make
For a kind of abundant, potential C1 raw materials, available for production of chemicals and fuel, the use for even substituting current fossil fuel is reduced
[Dalton Trans., 39,3347-3357 (2010)].However, due to CO2Centrosymmetric linear molecule (O=C=itself
O) structure, determines the 'inertia' of its chemical property, could only be reacted under special environment, such as higher temperature,
Pressure or special catalyst.Electrochemical reduction technology can utilize solar energy, wind energy, tide energy etc. under normal temperature and pressure conditionses
Green energy produced by regenerative resource, by CO2It is converted directly into useful chemicals and low-carbon fuel such as：Formic acid, methanol,
The hydrocarbon such as CO and methane, and its course of reaction has controllability, by changing electrolytic condition, such as electrode potential, temperature
Degree, electrolyte regulate and control whole reduction reaction system [Chem.Soc.Rev., 43 (2014) 631-675].In addition, electrochemical reaction
The features such as system also has compact conformation and is easy to scale [ChemSusChem, 4 (2011) 1301-1310], thus be considered as
It is to carry out CO2One of the conversion of the energy and utilization effective means.At present, in water solution system, metallic tin is considered as CO2Electricity
A kind of maximally effective catalyst of formic acid is produced in electronation.However, in electro-reduction process, it needs higher overpotential,
Energy efficiency is low, causes the waste [J.Am.Chem.Soc., 134 (2012) 1986-1989] of the energy.In addition, reacting
Metal tin catalyst is easily inactivated in journey, and stability is also far from demand [ChemSusChem, 4 for meeting actual industrialization
(2011)1301-1310].Therefore, the new CO with high activity, high selectivity and performance stabilization is developed2Electrochemical reduction
The problem of catalyst is diligent to be solved.
Bismuth is as a kind of environment-friendly while more economical a kind of metal again, is a kind of preferable catalyst choice
[J.Am.Chem.Soc., 136 (2014) 8361-8367].However, bismuth is used for CO2Electro-catalysis also originates in the research report of formic acid
But it is very rare.In view of the above-mentioned problems, we are successfully prepared micro-nano elemental metals Bi and apply high activity in the present invention, it is high
Selectivity and stable CO2Electro-catalysis reducing catalyst.Particularly the method for preparing catalyst is simple, mild condition, it is easy to work
Industry metaplasia is produced, for CO2The research of electrochemical reduction is significant.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of with high activity, the micro-nano elemental metals of high selectivity
Bismuth catalyst and preparation method thereof and its application in carbon dioxide catalysis reduction.The catalyst passes through simple aqueous solubilized
Restoring method is learned to be prepared.By Effective Regulation reaction condition (time, temperature), obtaining, there is micro-nano elemental metals Bi to urge
Agent, not only selectivity is high during carbon dioxide reduction, and can reduce overpotential, energy efficiency is improved, while effectively
Adjoint competition evolving hydrogen reaction during suppression carbon dioxide reduction.Selected gas-diffusion electrode is enriched by providing simultaneously
Hole and airwater mist cooling interface, reduce resistance to mass tranfer, improve CO2Utilization rate and conversion ratio, so as to improve faraday
Efficiency.Preparation method is simple, yield is big, be particularly suitable for industrialized production.
In order to solve the above-mentioned technical problem, the invention provides a kind of carbon dioxide electrochemical reduction catalyst, its feature
It is, including the micro-nano elemental metals bismuth catalyst synthesized by chemistry of aqueous solution restoring method.
Present invention also offers the preparation method of above-mentioned carbon dioxide electrochemical reduction catalyst, it is characterised in that bag
Include：Bismuth nitrate and nitric acid are dissolved in deionized water, Catalyst precursor solutions is obtained, Catalyst precursor solutions oil bath is added
Heat is simultaneously flowed back, and hydrazine hydrate reduction solution is added when rising to certain reaction temperature and is reduced, after reaction terminates, gained solid is washed
Wash and centrifuge, be dried in vacuo, obtain the elemental metals Bi carbon dioxide electrochemical reduction catalysts of micro-nano.
Preferably, described elemental metals bismuth has micro-nano multi-level structure.
Preferably, the concentration of bismuth nitrate is 0.2~0.5M in described Catalyst precursor solutions.
Preferably, described nitric acid is that the concentration of nitric acid in concentrated nitric acid, Catalyst precursor solutions is 0.5~0.75M.
Preferably, the concentration of hydrazine hydrate is 8~13M in described hydrazine hydrate reduction solution.
Preferably, described reaction temperature is 80~110 DEG C.
Preferably, the described reaction time is 30min~120min.
Preferably, described washing is for several times to neutral using deionized water and absolute ethyl alcohol washing.
Preferably, the volume ratio of described Catalyst precursor solutions and hydrazine hydrate reduction solution is 1: 2~1: 4.
Present invention also offers a kind of gas-diffusion electrode for being loaded with carbon dioxide electrochemical reduction catalyst, its feature
It is, including gas-diffusion electrode, above-mentioned Carbon dioxide electrochemical reduction catalysis is loaded with described gas-diffusion electrode
Agent.
Preferably, described gas-diffusion electrode is carbon paper, copper mesh, nickel screen and stainless (steel) wire.
Preferably, the size of described gas-diffusion electrode is 1cm × 1cm~3cm × 3cm, the dioxy loaded thereon
The load capacity for changing carbon electrochemical reduction catalyst is 2~4mg/cm2。
Preferably, described binding agent is that Nafion, polyvinyl alcohol, two kinds of PTFE or therein are combined.
Present invention also offers the system of the above-mentioned gas-diffusion electrode for being loaded with carbon dioxide electrochemical reduction catalyst
Preparation Method, it is characterised in that including：Above-mentioned carbon dioxide electrochemical reduction catalyst is distributed in aqueous isopropanol, surpassed
Sound obtains uniform catalyst slurry, adds binding agent Nafion solution in described catalyst slurry and ultrasonic disperse is equal
It is even, this mixed solution is coated in gas-diffusion electrode, is put into vacuum drying chamber or vacuum drying oven and dries, be loaded with
The gas-diffusion electrode of carbon dioxide electrochemical reduction catalyst.
Preferably, the dry ratio of described carbon dioxide electrochemical reduction catalyst and Nafion solution is 1: 1~3.5
∶1。
Preferably, the mass concentration of described Nafion solution is 2~5wt%.
Preferably, the load capacity of carbon dioxide electrochemical reduction catalyst is 2~4mg/ in described gas-diffusion electrode
cm2。
The present invention is micro-nano elemental metals Bi catalyst, is synthesized by chemistry of aqueous solution restoring method, passes through Effective Regulation
Catalyst synthesis condition, obtains the elemental metals Bi catalyst with micro-nano, can be greatly enhanced carbon dioxide electrochemistry
The Selectivity and activety of reduction, effectively suppresses the competition side reaction of liberation of hydrogen during carbon dioxide reduction；Selected gas diffusion
Electrode reduces resistance to mass tranfer by providing airwater mist cooling interface, improves CO2Utilization rate and conversion ratio, so as to improve method
Draw efficiency.
Compared with prior art, the beneficial effects of the invention are as follows：
(1) present invention is micro-nano simple substance bismuth catalyst.Synthesized, urged by Effective Regulation by chemistry of aqueous solution restoring method
Agent preparation condition, obtains the simple substance bismuth catalyst with micro-nano, the selectivity of carbon dioxide reduction can be greatly improved, and drops
Low CO2The overpotential of reduction, improves energy efficiency；Simultaneously effective suppress the competitive liberation of hydrogen pair during carbon dioxide reduction
Reaction.
(2) present invention uses gas-diffusion electrode to improve CO2The current density of reduction, and CO can be improved2's
Selectivity and conversion ratio, so as to improve faradic efficiency.
(3) preparation method of the present invention is simple, easy to operate, be easy to industrialization production.This invention is in carbon dioxide electrochemistry
The field such as reduction, carbon dioxide photoelectric reduction, carbon dioxide photo catalytic reduction has a good application prospect.
(4) micro-nano simple substance bismuth catalyst of the invention is accumulated by nano metal bismuth piece forms, brilliant with distinct (012)
Face, has high electro catalytic activity concurrently to carbon dioxide reduction and selectivity, particularly overpotential are low, can significantly improve to titanium dioxide
The energy efficiency that carbon is utilized.
Brief description of the drawings
Fig. 1 is that the gas-diffusion electrode in embodiment 1-3 loads simple substance Bi catalyst in CO2The 0.5M KHCO of saturation3In
Cyclic voltammetry curve figure.
Fig. 2 is that the gas-diffusion electrode in embodiment 2,4-5 loads simple substance Bi catalyst in CO2The 0.5M KHCO of saturation3
In cyclic voltammetry curve figure.
Fig. 3 is micro-nano simple substance Bi100-45Field emission scanning electron microscope figure FESEM.
Fig. 4 is that the gas-diffusion electrode load micro-nano simple substance Bi catalyst in example 1-3 is working electrode, in CO2It is full
The 0.5MKHCO of sum3The production formic acid faradic efficiency of 1 hour is electrolysed in solution.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
Embodiment 1
A kind of carbon dioxide electrochemical reduction catalyst, including the micro-nano simple substance synthesized by chemistry of aqueous solution restoring method
Metal bismuth catalyst.The preparation method of described carbon dioxide electrochemical reduction catalyst is：Weigh 2.5mmol five water nitric acid
Bismuth is added in beaker, is added after 10mL deionized waters and 0.5mL concentrated nitric acids (concentration is 14.4M), magnetic agitation 2h, is made nitric acid
Bismuth is dissolved in deionized water with nitric acid, obtains Catalyst precursor solutions；Solution is transferred to three-neck flask, oil bath pan pair is put into
Mixed solution carries out condensing reflux heating.When temperature rises to 100 DEG C, 30mL 8.5M N are added2H4·H2O is reduced, after
Continuous control temperature reacts 30min at 100 DEG C.After reaction terminates, natural cooling uses gained solid deionized water and anhydrous respectively
Ethanol is washed to neutrality and centrifuged, and with after 75 DEG C of vacuum drying of vacuum drying chamber, obtains the elemental metals Bi of micro-nano
(Bi100-30) carbon dioxide electrochemical reduction catalyst.
Embodiment 2
A kind of carbon dioxide electrochemical reduction catalyst, including the micro-nano simple substance synthesized by chemistry of aqueous solution restoring method
Metal bismuth catalyst.The preparation method of described carbon dioxide electrochemical reduction catalyst is：Weigh 2.5mmol five water nitric acid
Bismuth is added in beaker, is added after 10mL deionized waters and 0.5mL concentrated nitric acids (concentration is 14.4M), magnetic agitation 2h, is made nitric acid
Bismuth is dissolved in deionized water with nitric acid, obtains Catalyst precursor solutions；Solution is transferred to three-neck flask, oil bath pan pair is put into
Mixed solution carries out condensing reflux heating.When temperature rises to 100 DEG C, 30mL 8.5MN are added2H4·H2O is reduced, and continues to control
Temperature processed reacts 45min at 100 DEG C.After reaction terminates, gained solid is used deionized water and absolute ethyl alcohol by natural cooling respectively
Washing is to neutrality and centrifuges, and with after 75 DEG C of vacuum drying of vacuum drying chamber, obtains the elemental metals Bi of micro-nano
(Bi100-45) carbon dioxide electrochemical reduction catalyst.
Embodiment 3
A kind of carbon dioxide electrochemical reduction catalyst, including the micro-nano simple substance synthesized by chemistry of aqueous solution restoring method
Metal bismuth catalyst.The preparation method of described carbon dioxide electrochemical reduction catalyst is：Weigh 2.5mmol five water nitric acid
Bismuth is added in beaker, is added after 10mL deionized waters and 0.5mL concentrated nitric acids (concentration is 14.4M), magnetic agitation 2h, is made nitric acid
Bismuth is dissolved in deionized water with nitric acid, obtains Catalyst precursor solutions；Solution is transferred to three-neck flask, oil bath pan pair is put into
Mixed solution carries out condensing reflux heating.When temperature rises to 100 DEG C, 30mL 8.5MN are added2H4·H2O is reduced, and continues to control
Temperature processed reacts 60min at 100 DEG C.After reaction terminates, gained solid is used deionized water and absolute ethyl alcohol by natural cooling respectively
Washing is to neutrality and centrifuges, and with after 75 DEG C of vacuum drying of vacuum drying chamber, obtains the elemental metals Bi of micro-nano
(Bi100-60) carbon dioxide electrochemical reduction catalyst.
Embodiment 4
A kind of carbon dioxide electrochemical reduction catalyst, including the micro-nano simple substance synthesized by chemistry of aqueous solution restoring method
Metal bismuth catalyst.The preparation method of described carbon dioxide electrochemical reduction catalyst is：Weigh 2.5mmol five water nitric acid
Bismuth is added in beaker, is added after 10mL deionized waters and 0.5mL concentrated nitric acids (concentration is 14.4M), magnetic agitation 2h, is made nitric acid
Bismuth is dissolved in deionized water with nitric acid, obtains Catalyst precursor solutions；Solution is transferred to three-neck flask, oil bath pan pair is put into
Mixed solution carries out condensing reflux heating.When temperature rises to 110 DEG C, 30mL 8.5MN are added2H4·H2O is reduced, and continues to control
Temperature processed reacts 30min at 110 DEG C.After reaction terminates, gained solid is used deionized water and absolute ethyl alcohol by natural cooling respectively
Washing is to neutrality and centrifuges, and with after 75 DEG C of vacuum drying of vacuum drying chamber, obtains the elemental metals Bi of micro-nano
(Bi110-30) carbon dioxide electrochemical reduction catalyst.
Embodiment 5
A kind of carbon dioxide electrochemical reduction catalyst, including the micro-nano simple substance synthesized by chemistry of aqueous solution restoring method
Metal bismuth catalyst.The preparation method of described carbon dioxide electrochemical reduction catalyst is：Weigh 2.5mmol five water nitric acid
Bismuth is added in beaker, is added after 10mL deionized waters and 0.5mL concentrated nitric acids (concentration is 14.4M), magnetic agitation 2h, is made nitric acid
Bismuth is dissolved in deionized water with nitric acid, obtains Catalyst precursor solutions；Solution is transferred to three-neck flask, oil bath pan pair is put into
Mixed solution carries out condensing reflux heating.When temperature rises to 110 DEG C, 30mL 8.5MN are added2H4·H2O is reduced, and continues to control
Temperature processed reacts 45min at 110 DEG C.After reaction terminates, gained solid is used deionized water and absolute ethyl alcohol by natural cooling respectively
Washing is to neutrality and centrifuges, and with after 75 DEG C of vacuum drying of vacuum drying chamber, obtains the elemental metals Bi of micro-nano
(Bi110-45) carbon dioxide electrochemical reduction catalyst.
Accompanying drawing 1, Fig. 2 are the cyclic voltammetry scan figure under room temperature condition, and electrochemical property test is surveyed in electrochemical workstation
Test system (CHI660E, Shanghai Chen Hua company) is carried out, and test device is H-type groove, and electrolyte is the saturation of carbon dioxide
0.5MKHCO3The aqueous solution, the gas-diffusion electrode (GDE) of spraying catalyst is working electrode, and saturated calomel electrode is reference electricity
Pole, platinum electrode is auxiliary electrode, constitutes three-electrode system.It is respectively the carbon dioxide electricity in embodiment 1,2,3 shown in Fig. 1
Electronation catalyst.Fig. 1 illustrates that in 3 kinds of catalyst the catalytic activity of embodiment 2 preferably, and has larger dioxy
Change carbon reduction current density, as Bi100-45Catalyst.Shown in Fig. 2 be respectively embodiment 2, embodiment 4, embodiment 5 in
Carbon dioxide electrochemical reduction catalyst, equally, the catalytic activity of embodiment 2 preferably, show as higher reduction current density,
As Bi100-45。
Fig. 3 is micro-nano elemental metals Bi field emission scanning electron microscope figure FESEM, as shown in figure 3, prepared by the present invention
Bi100-45It is made up of the Bi pieces of submicron order.
Fig. 4 is the production formic acid faradic efficiency that embodiment 1-3 catalyst is electrolysed 1 hour under -1.45V current potentials.From figure
It can be seen that Bi100-45The formic acid faradic efficiency of catalyst is maximum, is 90%.
Claims (10)
1. a kind of carbon dioxide electrochemical reduction catalyst, it is characterised in that including what is synthesized by chemistry of aqueous solution restoring method
Micro-nano elemental metals bismuth catalyst.
2. the preparation method of the carbon dioxide electrochemical reduction catalyst described in claim 1, it is characterised in that including：By nitre
Sour bismuth and nitric acid are dissolved in deionized water, obtain Catalyst precursor solutions, by Catalyst precursor solutions oil bath heating and are returned
Stream, when rising to certain reaction temperature add hydrazine hydrate reduction solution reduced, react terminate after, by gained solid wash and from
The heart is separated, vacuum drying, obtains the elemental metals Bi carbon dioxide electrochemical reduction catalysts of micro-nano.
3. the preparation method of carbon dioxide electrochemical reduction catalyst as claimed in claim 2, it is characterised in that described list
Matter bismuth metal has micro-nano multi-level structure.
4. the preparation method of carbon dioxide electrochemical reduction catalyst as claimed in claim 2, it is characterised in that described urges
The concentration of bismuth nitrate is 0.2~0.5M in agent precursor solution.
5. the preparation method of carbon dioxide electrochemical reduction catalyst as claimed in claim 2, it is characterised in that described nitre
Acid is that the concentration of nitric acid in concentrated nitric acid, Catalyst precursor solutions is 0.5~0.75M.
6. the preparation method of carbon dioxide electrochemical reduction catalyst as claimed in claim 2, it is characterised in that described water
The concentration for closing hydrazine hydrate in hydrazine reducing solution is 8~13M.
7. the preparation method of carbon dioxide electrochemical reduction catalyst as claimed in claim 2, it is characterised in that described is anti-
It is 80~110 DEG C to answer temperature.
8. the preparation method of carbon dioxide electrochemical reduction catalyst as claimed in claim 2, it is characterised in that described is anti-
It is 30min~120min between seasonable.
9. a kind of gas-diffusion electrode for being loaded with carbon dioxide electrochemical reduction catalyst, it is characterised in that expand including gas
The carbon dioxide electrochemical reduction catalyst described in claim 1 is loaded with scattered electrode, described gas-diffusion electrode.
10. the preparation method of the gas-diffusion electrode for being loaded with carbon dioxide electrochemical reduction catalyst described in claim 9,
It is characterised in that it includes：Carbon dioxide electrochemical reduction catalyst described in claim 1 is distributed in aqueous isopropanol,
Ultrasound obtains uniform catalyst slurry, adds binding agent Nafion solution in described catalyst slurry and ultrasonic disperse is equal
It is even, this mixed solution is coated in gas-diffusion electrode, is put into vacuum drying chamber or vacuum drying oven and dries, be loaded with
The gas-diffusion electrode of carbon dioxide electrochemical reduction catalyst.
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| CN109603806A (en) * | 2019-01-16 | 2019-04-12 | 哈尔滨工业大学 | A kind of Bi catalyst and preparation method thereof |
| CN109930165A (en) * | 2017-12-19 | 2019-06-25 | 中国科学院大连化学物理研究所 | Bi/C method for preparing catalyst for carbon dioxide electro-catalysis reduction |
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